JPH03193490A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPH03193490A JPH03193490A JP1335730A JP33573089A JPH03193490A JP H03193490 A JPH03193490 A JP H03193490A JP 1335730 A JP1335730 A JP 1335730A JP 33573089 A JP33573089 A JP 33573089A JP H03193490 A JPH03193490 A JP H03193490A
- Authority
- JP
- Japan
- Prior art keywords
- mixture
- melting point
- color
- coupling compound
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims description 43
- 230000008018 melting Effects 0.000 claims description 40
- 238000004040 coloring Methods 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 35
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000243 solution Substances 0.000 abstract description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 5
- 239000000049 pigment Substances 0.000 abstract description 5
- 239000000725 suspension Substances 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 239000012188 paraffin wax Substances 0.000 abstract description 4
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005562 fading Methods 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 6
- 238000010168 coupling process Methods 0.000 abstract 6
- 238000005859 coupling reaction Methods 0.000 abstract 6
- 238000002360 preparation method Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 14
- 238000003860 storage Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- -1 bisphenol A Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004042 decolorization Methods 0.000 description 5
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- FIPTYOFKSOWKTF-UHFFFAOYSA-N 1,2-diphenoxybenzene Chemical compound C=1C=CC=C(OC=2C=CC=CC=2)C=1OC1=CC=CC=C1 FIPTYOFKSOWKTF-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- BZMWYTDVUYRVEI-UHFFFAOYSA-N 1,4-bis(4-methylphenoxy)benzene Chemical compound C1=CC(C)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(C)C=C1 BZMWYTDVUYRVEI-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- OAGNKYSIOSDNIG-UHFFFAOYSA-N 1-methyl-3-[2-(3-methylphenoxy)ethoxy]benzene Chemical compound CC1=CC=CC(OCCOC=2C=C(C)C=CC=2)=C1 OAGNKYSIOSDNIG-UHFFFAOYSA-N 0.000 description 1
- JWSWULLEVAMIJK-UHFFFAOYSA-N 1-phenylmethoxynaphthalene Chemical compound C=1C=CC2=CC=CC=C2C=1OCC1=CC=CC=C1 JWSWULLEVAMIJK-UHFFFAOYSA-N 0.000 description 1
- HUOKHAMXPNSWBJ-UHFFFAOYSA-N 2'-chloro-6'-(diethylamino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Cl)=C(C)C=C1OC1=CC(N(CC)CC)=CC=C21 HUOKHAMXPNSWBJ-UHFFFAOYSA-N 0.000 description 1
- LGERKUYJCZOBTB-UHFFFAOYSA-N 2-hydroxy-5-phenylbenzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1 LGERKUYJCZOBTB-UHFFFAOYSA-N 0.000 description 1
- SUCTVKDVODFXFX-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfonyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(S(=O)(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 SUCTVKDVODFXFX-UHFFFAOYSA-N 0.000 description 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- BPLKDVGMXNZCQO-UHFFFAOYSA-N benzyl 4-phenylmethoxybenzoate Chemical compound C=1C=C(OCC=2C=CC=CC=2)C=CC=1C(=O)OCC1=CC=CC=C1 BPLKDVGMXNZCQO-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RQAQWBFHPMSXKR-UHFFFAOYSA-N n-(4-chlorophenyl)-3-(phosphonooxy)naphthalene-2-carboxamide Chemical compound OP(O)(=O)OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=C(Cl)C=C1 RQAQWBFHPMSXKR-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は感熱記録体に関するものであり、更に詳しく述
べるならば、発色画像の経時安定性、耐熱性、および耐
湿保存性に優れた感熱記録体に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a heat-sensitive recording medium, and more specifically, a heat-sensitive recording medium that has excellent color image stability over time, heat resistance, and moisture-resistant storage stability. It's about the body.
通常、無色または淡色のロイコ染料などの染料前駆体と
、フェノール類、特にビスフェノールAなどの顕色剤と
の加熱発色反応を利用した感熱記録体は、例えば特公昭
43−4160号、特公昭45−14039号、特公昭
48−27736号等に発表され、広く実用化されてい
る。このような感熱記録体は、単に加熱するだけで発色
画像が形成され、記録装置を比較的コンパクトなものに
することができるなどの利点を有しているため、近年、
各種情報記録材料として広範囲に使用されるようになっ
ている。特に、感熱記録体を用いる感熱ファクシミリ、
および感熱プリンター等は、その装置の改良が進み、従
来は難しいとされていた高速の印字、および高速の画像
の形成が可能となったため、その使用範囲は急速に拡大
している。このような使用範囲の拡大にともない、加熱
により発色した画像が経時的に消色するという問題、お
よび、高温下、または高湿度下でこの消色が加速される
という問題の解消が望まれるようになってきている。発
色画像の消色抑制するために、従来量も一般的に行なわ
れてきた手法は、ゴムやプラスチック類の酸化による劣
化を防止する目的に開発され使用されている酸化防止剤
、特にヒドロキシル基で置換されたベンゼン環を有する
化合物であって、さらにそのオルト位がターシャリ−ブ
チル基、シクロヘキシル基、フェニル基、およびアダマ
ンチル基などで代表される嵩高い置換基で置換されたヒ
ンダードフェノール類を感熱発色層中に併用することで
ある。このような技術は、例えば特開昭57−1513
94号、同58−160191号、同58−69096
号、同59−2884号、同59−95190号、同6
0−22288号、同60−255485号、同61−
44686号、同62−169683号、同63−17
081号、特開平1−249385号、特開平1−24
9385号などに具体的に開示されている。Usually, heat-sensitive recording materials that utilize a heated color-developing reaction between a colorless or light-colored dye precursor such as a leuco dye and a color developer such as phenols, particularly bisphenol A, are disclosed in, for example, Japanese Patent Publication No. 43-4160, Japanese Patent Publication No. 45 It was published in Japanese Patent Publication No. 14039, Japanese Patent Publication No. 48-27736, etc., and has been widely put into practical use. Such heat-sensitive recording materials have the advantage that a colored image can be formed by simply heating them, and the recording device can be made relatively compact, so in recent years, they have become popular.
It has come to be widely used as a variety of information recording materials. In particular, thermal facsimile using a thermal recording medium,
BACKGROUND ART The range of use of thermal printers and other devices is rapidly expanding as improvements have progressed and it has become possible to perform high-speed printing and high-speed image formation, which was previously considered difficult. With the expansion of the scope of use, it is desirable to solve the problem of images that are colored by heating becoming discolored over time, and that this discoloration is accelerated under high temperature or high humidity. It is becoming. In order to suppress the decolorization of colored images, the conventional method has been to use antioxidants, especially those with hydroxyl groups, that have been developed and used to prevent the deterioration of rubber and plastics due to oxidation. Hindered phenols, which are compounds with a substituted benzene ring and whose ortho position is further substituted with bulky substituents such as tertiary-butyl, cyclohexyl, phenyl, and adamantyl groups, are heat-sensitive. It is used in combination in the coloring layer. Such technology is disclosed in, for example, Japanese Patent Application Laid-open No. 57-1513.
No. 94, No. 58-160191, No. 58-69096
No. 59-2884, No. 59-95190, No. 6
No. 0-22288, No. 60-255485, No. 61-
No. 44686, No. 62-169683, No. 63-17
No. 081, JP-A-1-249385, JP-A-1-24
This is specifically disclosed in No. 9385 and the like.
感熱記録体に形成された発色画像の経時的消色を抑制す
るために用いられる上記ヒンダードフェノール類は、こ
れを感熱発色層中に添加すると、消色の速度は確かに抑
制される傾向が認められるが、その程度は少量の添加で
は決して十分ではなく、それを多量に用いると、感熱記
録体の白色度や感度を低下させるという問題点があり、
また、同一薬品を用いた場合でも、特に添加量が少ない
場合には、その消色抑制効果に再現性が欠けるという問
題点があった。The above-mentioned hindered phenols, which are used to suppress the decoloring of colored images formed on thermosensitive recording materials over time, do tend to suppress the speed of decoloring when added to the thermosensitive coloring layer. However, adding a small amount is by no means sufficient, and if a large amount is used, there is a problem that the whiteness and sensitivity of the heat-sensitive recording medium will be reduced.
Further, even when the same chemicals are used, there is a problem in that the decolorization inhibiting effect lacks reproducibility, especially when the amount added is small.
本発明は、発色画像の経時的消色を効率よく、かつ再現
性よく抑制することのできる感熱記録体を提供しようと
するものである。An object of the present invention is to provide a heat-sensitive recording material that can efficiently and reproducibly suppress decolorization of a colored image over time.
本発明の感熱記録体は、シート状基体と、このシート状
基体の少なくとも一面に形成され、かつ、無色または淡
色の染料前駆体と、この染料前駆体と加熱下に反応して
これを発色させる顕色剤とを含む感熱発色層とを有し、
前記顕色剤が、160℃未満の融点を有する少なくとも
1種の顕色性化合物と、160℃以上の融点を有する少
なくとも1種の顕色性化合物との分子レベルにおける混
合物からなることを特徴とするものである。The heat-sensitive recording material of the present invention includes a sheet-like substrate, a colorless or light-colored dye precursor formed on at least one surface of the sheet-like substrate, and a dye precursor that reacts with the dye precursor under heating to develop color. It has a heat-sensitive coloring layer containing a color developer,
The color developer is characterized in that it consists of a mixture at the molecular level of at least one color developer compound having a melting point of less than 160°C and at least one color developer compound having a melting point of 160°C or higher. It is something to do.
本発明の感熱記録体において、感熱発色層中に含まれる
顕色剤が、160℃未満の融点を有する少なくとも1種
の顕色性化合物(低融点顕色性化合物)と、160℃以
上の融点を有する少なくとも一種の顕色性化合物(高融
点顕色性化合物)との分子レベルにおける混合物を用い
ることにより、ヒンダードフェノール類の分散物を使用
する従来方法を格段に凌駕する消色抑制が得られる。ま
た、低融点顕色性化合物として、融点160℃未満のビ
スフェノール八を用いると上記効果が一層顕著である。In the heat-sensitive recording material of the present invention, the color developer contained in the heat-sensitive color forming layer includes at least one color developer compound having a melting point of less than 160°C (low melting point color developer compound) and a melting point of 160°C or more. By using a mixture at the molecular level with at least one color developing compound (high melting point color developing compound) having It will be done. Further, when bisphenol 8, which has a melting point of less than 160° C., is used as the low melting point color developing compound, the above effect is even more remarkable.
融点160℃未満の顕色性化合物の2種のみを分子レベ
ルで混合したものを用いて得られる感熱記録体は、白色
度が低いという欠点を示し、また160℃以上の融点を
有する顕色性化合物2種のみの分子レベルにおける混合
物を用いると、得られる感熱記録体の感度が不十分であ
るという欠点を示す。A heat-sensitive recording material obtained by using a mixture of only two types of color developer compounds with a melting point of less than 160°C at a molecular level has a drawback of low whiteness, and a color developer with a melting point of 160°C or more has a disadvantage of low whiteness. The use of a mixture of only two types of compounds at the molecular level shows the drawback that the sensitivity of the resulting heat-sensitive recording material is insufficient.
前記低融点顕色性化合物、特にビスフェノールAと、高
融点顕色性化合物との分子レベルにおける混合物とは、
例えば両者の混合物を加熱溶融した後、その温度を下げ
結晶化させて得られる混合物、および、より実用的には
両者の混合物を、それを溶解し得る溶媒、例えばエタノ
ール又はアセトンに溶解し、この溶液に両者を不溶また
は難溶な溶媒、例えば水を加え再結晶することにより得
られる混合物を意味する。このようにして得られた低融
点顕色性化合物と高融点顕色性化合物との混合物は、こ
れを−旦融点以上1どしてこれを融解すると、この溶融
体の温度を低下させても再び結晶体になるのに非常に長
い時間がかかることが観測される。この現象が発色した
画像の消色速度を抑制する効果と深く結びついているも
のと考えられるが、その消色抑制機構については、未だ
十分には明らかにされていない。The mixture at the molecular level of the low melting point color developer compound, especially bisphenol A, and the high melting point color developer compound is:
For example, the mixture obtained by heating and melting a mixture of the two and then lowering the temperature to crystallize, or more practically, dissolving the mixture of both in a solvent that can dissolve it, such as ethanol or acetone, and It means a mixture obtained by adding a solvent in which both are insoluble or poorly soluble, such as water, to a solution and recrystallizing the two. The mixture of the low melting point color developing compound and the high melting point color developing compound obtained in this way can be melted by heating it to above the melting point, even if the temperature of the melt is lowered. It is observed that it takes a very long time to crystallize again. It is thought that this phenomenon is deeply connected to the effect of suppressing the speed of decolorization of a colored image, but the mechanism of suppressing decolorization has not yet been fully clarified.
融点160℃未満の顕色性化合物としては、例えば以下
のようなものがあげられる。すなわちビスフェノールA
(1点156℃)、p−ヒドロキシ安息香酸ベンジル
(特開昭52−140483号、融点110℃)、4−
ヒドロキシ−4′−イソプロビルオキシジフェニルスル
ホン(特開昭60−13852号、融点129℃)、お
よび1.7−ビス(ヒドロキシフェニルチオ)−3,5
−ジオキサへブタン(特開昭59−52694号、融点
100℃)、などである。Examples of the color developing compound having a melting point of less than 160°C include the following. i.e. bisphenol A
(1 point 156°C), benzyl p-hydroxybenzoate (JP-A-52-140483, melting point 110°C), 4-
Hydroxy-4'-isoprobyloxydiphenylsulfone (JP-A-60-13852, melting point 129°C), and 1,7-bis(hydroxyphenylthio)-3,5
-dioxahebutane (JP-A-59-52694, melting point 100°C), etc.
また、融点160℃以上の顕色性化合物としては、例え
ば以下のようなものをあげることができる。Furthermore, examples of the color developing compound having a melting point of 160° C. or higher include the following.
すなわち、ビス(4−ヒドロキシフェニル)メタン(ビ
スフェノールF、融点160℃)、1・1−ビス(4’
−ヒドロキシフェニル)−1−7,エニルーエタン(融
点188℃)、i、i−ビス(4′−ヒドロキシフェニ
ル)シクロヘキサン(融点175℃)、4−フェニルフ
ェノール(融点164℃)、ビス(3’ 、5’ −
ジメチル−4−ヒドロキシフェニル)スルホン(1点2
98℃)、ビス(4−ヒドロキシフェニル)スルホン(
融点248℃)、4゜4′−ビフェノール(融点278
℃)、4−ヒドロキシビフェニル−3−カルボン酸(融
点217℃)、サリチル酸誘導体亜鉛塩、およびオキシ
ナフトエ酸亜鉛などである。Namely, bis(4-hydroxyphenyl)methane (bisphenol F, melting point 160°C), 1,1-bis(4'
-hydroxyphenyl)-1-7, enyl ethane (melting point 188°C), i,i-bis(4'-hydroxyphenyl)cyclohexane (melting point 175°C), 4-phenylphenol (melting point 164°C), bis(3', 5'-
dimethyl-4-hydroxyphenyl) sulfone (1 point 2
98°C), bis(4-hydroxyphenyl)sulfone (
4°4'-biphenol (melting point 278°C), 4°4'-biphenol (melting point 278°C)
C), 4-hydroxybiphenyl-3-carboxylic acid (melting point 217C), salicylic acid derivative zinc salt, and zinc oxynaphthoate.
本発明の感熱記録体の感熱発色層は、染料前駆体と、高
融点顕色性化合物と低融点顕色性化合物との分子レベル
における混合物からなる顕色剤と、および、必要に応じ
て増感剤として知られる熱可融性有機化合物を含むもの
である。また感熱発色層は、無機顔料を含んでいること
が好ましく、更に必要に応じて、ワックス類を含んでい
てよい。The thermosensitive color forming layer of the thermosensitive recording material of the present invention comprises a dye precursor, a color developer consisting of a mixture at the molecular level of a high melting point color developer compound and a low melting point color developer compound, and, if necessary, an additive. It contains a heat-fusible organic compound known as a sensitizer. Further, the heat-sensitive coloring layer preferably contains an inorganic pigment, and may further contain waxes if necessary.
更に感熱発色層は、これらの成分を結着し、支持体に固
着する為のバインダーを含んでいる。Furthermore, the thermosensitive color forming layer contains a binder for binding these components and fixing them to the support.
感熱発色層中の染料前駆体の含有率は、一般に5〜20
重量%であり、顕色剤混合物の含有率は一般に10〜4
0重量%である。低融点顕色性化合物(例えばビスフェ
ノールA)には、それに対し3〜100重量%、特に好
ましくは5〜50重量%の高融点顕色性化合物を分子レ
ベルで混合させるのが好ましい。高融点顕色性化合物の
量が、3%未満では消色抑制効果が十分ではなく、また
100%を越えると感熱記録体の白色度が低下したり、
感度が低下したりする欠点が見られるようになる。また
バインダーの含有率は一般に5〜20重量%であり、白
色顔料およびワックス類が含まれるときは、それらの含
有率は一般にそれぞれ10〜50重量%、および5〜3
0重量%程度である。The content of the dye precursor in the thermosensitive coloring layer is generally 5 to 20
% by weight, and the content of the developer mixture is generally between 10 and 4
It is 0% by weight. It is preferable to mix 3 to 100% by weight, particularly preferably 5 to 50% by weight, of a high melting point color developing compound with the low melting point color developing compound (for example, bisphenol A) at the molecular level. If the amount of the high-melting point color developing compound is less than 3%, the effect of inhibiting color fading will not be sufficient, and if it exceeds 100%, the whiteness of the heat-sensitive recording material may decrease.
There are some drawbacks such as decreased sensitivity. The binder content is generally 5 to 20% by weight, and when white pigments and waxes are included, their content is generally 10 to 50% by weight and 5 to 3% by weight, respectively.
It is about 0% by weight.
染料前駆体としては、従来感熱発色層に用いられている
ロイコ染料から選ぶことができ、例えば以下のものがあ
げられる。すなわち、クリスタルバイオレットラクトン
、3− (N−エチル−N−イソペンチルアミノ)−6
−メチル−7−アニリノフルオラン、3−ジエチルアミ
ン−6−メチル=7−アニリノフルオラン、3−ジエチ
ルアミノ−6−メチル−7−(o、p−ジメチルアニリ
ノ)フルオラン、3− (N−エチル−p−トルイジノ
)−6−メチル−7−アニリノフルオラン、3−ピロリ
ジノ−6−メチル−7−アニリノフルオラン、3−ジブ
チルアミノ−6−メチル−7−アニリノフルオラン、3
−(N−シクロへキシル−N−メチルアミノ)−6−メ
チル−7−アニリノフルオラン、3−ジエチルアミノ−
7−(0−クロロアニリノ)フルオラン、3−ジエチル
アミノ−7−(m−)リフルオロメチルアニリノ)フル
オラン3−ジエチルアミノ−6−メチル−7−クロロフ
ルオラン、3−ジエチルアミノ−6−メチルフルオラン
、および3−シクロへキシルアミノ−6−クロロフルオ
ランなどであり、これらはその2種以上を混合して用い
てもよく、或は単独で用いてもよい。The dye precursor can be selected from leuco dyes conventionally used in thermosensitive coloring layers, including the following. namely, crystal violet lactone, 3-(N-ethyl-N-isopentylamino)-6
-Methyl-7-anilinofluorane, 3-diethylamine-6-methyl 7-anilinofluorane, 3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluorane, 3-(N -ethyl-p-toluidino)-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3
-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane, 3-diethylamino-
7-(0-chloroanilino)fluoran, 3-diethylamino-7-(m-)lifluoromethylanilino)fluoran 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-6-methylfluoran, and 3-cyclohexylamino-6-chlorofluorane, and these may be used in combination of two or more thereof, or may be used alone.
本発明の感熱発色層には、前述のように増感剤が含まれ
ていてもよく、このような増感剤としては、好ましくは
80〜120℃の範囲内に融点を有する一群の特定の有
機化合物が用いられ、それらの代表的例としては1−ヒ
ドロキシ−2−ナフトエ酸フェニルエステル(特開昭5
7−191089号)、p−ベンジルビフェニル(同6
0−82382号)、ベンジルナフチルエーテル(同5
8−87094号)、ジベンジルテレフタレート (同
58−98285号)、p−ベンジルオキシ安息香酸ベ
ンジル(同57−201691号)、炭酸ジフェニノペ
炭酸ジトリル(同5g−136489号)、m−ターフ
ェニル(同57−89994号)、1.2−ビス(m−
トリルオキシ)エタン(同60−56588号)、1.
5−ビス(p−メトキシフェノキシ)−3−オキサベン
クン(同62−181183号)、1.4−ビス(p−
トリルオキシ)ベンゼン(特[1[63−276186
号)、および1.2−ジフェノキシベンゼン(特願平1
−84788号)などをあげることができる。The heat-sensitive color forming layer of the present invention may contain a sensitizer as described above, and such a sensitizer preferably includes a group of specific sensitizers having a melting point within the range of 80 to 120°C. Organic compounds are used, a typical example of which is 1-hydroxy-2-naphthoic acid phenyl ester (JP-A-5
7-191089), p-benzylbiphenyl (No. 6
0-82382), benzyl naphthyl ether (No. 5
No. 8-87094), dibenzyl terephthalate (No. 58-98285), benzyl p-benzyloxybenzoate (No. 57-201691), dipheninope ditolyl carbonate (No. 5g-136489), m-terphenyl (No. 57-136489), 57-89994), 1,2-bis(m-
Tolyloxy)ethane (No. 60-56588), 1.
5-bis(p-methoxyphenoxy)-3-oxabencune (No. 62-181183), 1,4-bis(p-
Tolyloxy)benzene (Special [1[63-276186
), and 1,2-diphenoxybenzene (Patent Application No. 1999), and 1,2-diphenoxybenzene
-84788).
又、感熱発色層中に用いられる有機又は無機の顔料とし
ては、炭酸カルシウム、シリカ、酸化亜鉛、酸化チタン
、水酸化アルミニウム、水酸化亜鉛、硫酸バリウム、ク
レー、タルク、および表面処理された炭酸カルシウムや
シリカ等の無機系微粉末、並びに、尿素−ホルマリン樹
脂、スチレン/メタクリル酸共重合体、およびポリスチ
レン樹脂等の有機系の微粉末などを挙げることができる
。Organic or inorganic pigments used in the heat-sensitive coloring layer include calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, and surface-treated calcium carbonate. Examples include inorganic fine powders such as and silica, and organic fine powders such as urea-formalin resin, styrene/methacrylic acid copolymer, and polystyrene resin.
更に本発明の感熱発色層は、種々のワックス類を必要に
応じて含有していてもよい。それらはパラフィン、アミ
ド系ワックス、ビスイミド系ワックス、高級脂肪酸の金
属塩など公知のものから選ぶことができる。又、前記バ
インダーとしては、種々の分子量のポリビニルアルコー
ル、デンプン及びその誘導体、メトキシセルロース、カ
ルボキシメチルセルロース、メチルセルロース、エチル
セルロース等のセルロース誘導体、ポリアクリル酸ソー
ダ、ポリビニルピロリドン、アクリル酸アミド/アクリ
ル酸エステル共重合体、アクリル酸アミド/アクリル酸
エステル/メタクリル酸3元共重合体、スチレン/無水
マレイン酸共重合体アルカリ塩、ポリアクリルアミド、
アルギン酸ソーダ、ゼラチン、カゼイン等のような水溶
性高分子化合物、並びにポリ酢酸ビニル、ポリウレタン
、スチレン/ブタジェン共重合体、ポリアクリル酸、ポ
リアクリル酸エステル、塩化ビニル/酢酸ビニル共重合
体、ポリブチルメタクリレート、エチレン/酢酸ビニル
共重合体、スチレン/ブタジェン/アクリル系共重合体
等のラテックスを用いることができる。Furthermore, the heat-sensitive coloring layer of the present invention may contain various waxes as required. They can be selected from known ones such as paraffin, amide wax, bisimide wax, and metal salts of higher fatty acids. The binders include polyvinyl alcohols of various molecular weights, starches and their derivatives, cellulose derivatives such as methoxycellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, and acrylic acid amide/acrylic ester copolymers. Coalescence, acrylic amide/acrylic ester/methacrylic acid ternary copolymer, styrene/maleic anhydride copolymer alkali salt, polyacrylamide,
Water-soluble polymer compounds such as sodium alginate, gelatin, casein, etc., as well as polyvinyl acetate, polyurethane, styrene/butadiene copolymer, polyacrylic acid, polyacrylic ester, vinyl chloride/vinyl acetate copolymer, polybutyl Latex such as methacrylate, ethylene/vinyl acetate copolymer, styrene/butadiene/acrylic copolymer, etc. can be used.
上記各成分を所定の配合比で混合し、得られた感熱発色
層用塗布液を、紙、表面に粘土プラスチックなどを塗工
したコーテツド紙、主としてプラスチック材料から作ら
れた合成紙、およびプラスチックフィルムなどから選ば
れたシート状基体の1面上に塗布し、乾燥して感熱発色
層を形成する。The above components are mixed in a predetermined ratio, and the resulting heat-sensitive coloring layer coating liquid is applied to paper, coated paper whose surface is coated with clay plastic, synthetic paper made mainly from plastic materials, and plastic film. It is coated on one side of a sheet-like substrate selected from the following and dried to form a heat-sensitive coloring layer.
塗布液の塗工量は、それが乾燥した状態で1〜10g/
m′となるようにすることが好ましく、2〜7g /
m″が特に好ましい。本発明の感熱記録体は、その発色
画像が、高融点顕色性化合物を用いない場合に比べては
もちろん、例えば画像保存性改良のためにヒンダードフ
ェノール類を添加した感熱発色層を有する感熱記録体に
比較しても、なお−層経時的な消色が少なく、かつ加湿
雰囲気下や、加湿雰囲気下でも優れた記録保存性を示す
。The coating amount of the coating liquid is 1 to 10 g/dry state.
It is preferable to make it m', 2 to 7 g /
m'' is particularly preferable.The heat-sensitive recording material of the present invention has a color-developed image that is not only the case where a high melting point color developing compound is not used, but also the case where a hindered phenol is added to improve image storage stability. Even when compared to a thermosensitive recording material having a thermosensitive coloring layer, the layer exhibits less discoloration over time and exhibits excellent recording storage properties even in a humidified atmosphere.
以下に実施例により本発明を更に説明する。なお特に断
らない限り「部」、および「%」は「重量部」および「
重量%」を表す。The present invention will be further explained below with reference to Examples. Unless otherwise specified, "parts" and "%" refer to "parts by weight" and "%".
% by weight.
顕色性化合物混合物の調製例1
ビスフェノールA30gと、1.1−ビス(4′−ヒド
ロキシフェニル)−1−フェニル−エタン(融点188
℃)3gとを、30m1のアセトンに溶かし、これを加
熱しながら300艷の水を加えた。形成された白色懸濁
液を冷却後ろ過することにより32、8 gの顕色性化
合物分子混合物を得た。Preparation Example 1 of Color Developing Compound Mixture 30 g of bisphenol A and 1,1-bis(4'-hydroxyphenyl)-1-phenyl-ethane (melting point 188
℃) was dissolved in 30ml of acetone, and 300ml of water was added while heating. The white suspension formed was filtered after cooling to obtain 32.8 g of a mixture of color developer compound molecules.
顕色性化合物混合物の調製例2
ビスフェノールA30 gと、1,1−ビス(4′−ヒ
ドロキシフェニル)シクロヘキサン(融点175℃)3
gとを、30rdのアセトンに溶かし、これを加熱しな
がら300rnlの水を加えた。形成された白色懸濁液
を冷却後ろ過することにより、32.8gの顕色性化合
物分子混合物を得た。Preparation Example 2 of Color Developing Compound Mixture 30 g of bisphenol A and 30 g of 1,1-bis(4'-hydroxyphenyl)cyclohexane (melting point 175°C)
g was dissolved in 30rd acetone, and 300rnl of water was added to this while heating. The white suspension formed was filtered after cooling, yielding 32.8 g of a mixture of color developer compound molecules.
顕色性化合物混合物の調製例3
ビスフェノールA30gと、ビス(4−ヒドロキシフェ
ニル)スルホン(融点248℃)3gとを、30mj!
のアセトンに溶かし、これを加熱しながら300mj!
の水を加えた。形成された白色懸濁液を冷却後ろ過する
ことにより、32.2 gの顕色性化合物分子混合物を
得た。Preparation Example 3 of Color Developing Compound Mixture 30 g of bisphenol A and 3 g of bis(4-hydroxyphenyl)sulfone (melting point 248°C) were mixed into 30 mj!
Dissolve it in acetone and heat it to 300mj!
of water was added. The white suspension formed was filtered after cooling, yielding 32.2 g of a mixture of color developer compound molecules.
顕色性化合物混合物の調製例4
4−ヒドロキシ−4′−イソプロピルオキシジフェニル
スルホン30gと、1.1−ビス(4′ヒドロキシフエ
ニル)−1−フェニル−エタン3gとを、30−のアセ
トンに溶かし、これを加熱しながら300−の水を加え
た。形成された白色懸濁液を冷却後ろ過することにより
、32.8 gの顕色性化合物分子混合物を得た。Preparation Example 4 of Color Developing Compound Mixture 30 g of 4-hydroxy-4'-isopropyloxydiphenyl sulfone and 3 g of 1,1-bis(4'hydroxyphenyl)-1-phenyl-ethane were dissolved in 30-acetone. After melting, 300ml of water was added while heating. The white suspension formed was filtered after cooling, yielding 32.8 g of a mixture of color developer compound molecules.
実施例1 下記の操作により感熱記録紙を調製した。Example 1 A thermosensitive recording paper was prepared by the following procedure.
■ 分散液Aの調製
成分 量(部)
3−(ジブチルアミノ)−620
−メチル−7−アニリツフル
オラン
ポリビニルアルコール10%液 10水
70この組成
物をサンドグラインダーで平均粒径1pまで粉砕した。■ Ingredients for preparing dispersion A Amount (parts) 3-(dibutylamino)-620-methyl-7-anilite fluoran polyvinyl alcohol 10% solution 10 water
70 This composition was ground with a sand grinder to an average particle size of 1 p.
■ 分散液Bの調製
成分 量(部)
顕色性化合物分子混合物
(調製例1)11
パラベンジルビフェノール 10ポリビニル
アルコール10%1llt 10水
70この組成
物をサンドグラインダーで平均粒径1烏まで粉砕した。■ Ingredients for preparing dispersion B Amount (parts) Color-developing compound molecular mixture (Preparation Example 1) 11 Parabenzylbiphenol 10 Polyvinyl alcohol 10% 1llt 10 Water
70 This composition was ground to an average particle size of 1 mm using a sand grinder.
■ 感熱発色層の調製
上記A液40部、B液160部、炭酸カルシウム顔料4
0部、30%パラフィン分散液20部、10%ポリビニ
ルアルコール水溶液180部を混合、攪拌し、塗工用液
とした。この塗工液を、50g/m’の原紙に乾燥後の
塗布量が7.0g/m″となるように塗布乾燥して感熱
発色層を形成して感熱記録紙を得た。■ Preparation of thermosensitive coloring layer 40 parts of the above liquid A, 160 parts of liquid B, 4 parts of calcium carbonate pigment
0 parts, 20 parts of a 30% paraffin dispersion, and 180 parts of a 10% polyvinyl alcohol aqueous solution were mixed and stirred to prepare a coating liquid. This coating liquid was coated on a 50 g/m' base paper so that the coated amount after drying was 7.0 g/m'' and dried to form a heat-sensitive coloring layer to obtain a heat-sensitive recording paper.
上記の様にして得られた感熱記録紙を、スーパーカレン
ダーによって処理し、その表面の平滑度をベック平滑度
計で測定した平滑度が800〜1200秒になるように
した。こうして得られた試料について、発色濃度の測定
、および発色部の経時、耐熱、耐湿保存性の評価試験を
行なった。The heat-sensitive recording paper obtained as described above was treated with a supercalender so that the surface smoothness was 800 to 1200 seconds as measured by a Beck smoothness meter. The samples thus obtained were subjected to measurement of color density and evaluation tests of aging, heat resistance, and moisture resistance of the color development area.
発色濃度および白紙部濃度の測定
記録感度の測定には東洋精機装態傾斜試験器を用い、感
熱発色層を温度130℃、圧力2.5 kg / ct
lでlQQmsec間、また、温度110℃で100m
5ec間試料を加熱し、それぞれの発色濃度をマクベス
濃度計RD−914で測定し、その測定値をもって、感
熱記録紙の初期発色能を代表する値とした。Measurement and recording of color density and blank area density To measure sensitivity, a Toyo Seiki Sosho tilt tester was used, and the heat-sensitive coloring layer was heated at a temperature of 130°C and a pressure of 2.5 kg/ct.
1 for 1QQmsec, and 100m at a temperature of 110℃
The samples were heated for 5 ec, and the color density of each was measured using a Macbeth densitometer RD-914, and the measured value was taken as a value representative of the initial color development ability of the thermosensitive recording paper.
発色部保存性の評価
・経時保存性二上記の方法で発色させた試験片を居室内
に放置し、1週間後の色濃度を上記マクベス濃度計で測
定し、その値の初期発色濃度に対するパーセンテージに
より感熱記録紙の経時保存率(%)を表示した。Evaluation of preservability of colored parts/preservability over time 2. The test pieces developed using the above method are left in a living room, and the color density after one week is measured using the Macbeth densitometer mentioned above, and the percentage of that value with respect to the initial color density is determined. The storage rate (%) of the thermal recording paper over time was displayed.
・耐熱保存性:上記の方法で発色させた試験片を、50
℃に調整した乾燥器内に24時間放置し、その後の色濃
度を上記マクベス濃度計で測定し、その値の初期発色濃
度に対するパーセンテージをもって感熱記録紙の耐熱保
存率(%)を表示した。・Heat-resistant storage stability: The test piece colored by the above method was
The paper was left in a dryer adjusted to ℃ for 24 hours, and then the color density was measured using the above-mentioned Macbeth densitometer, and the heat-resistant storage rate (%) of the thermal recording paper was expressed as a percentage of the initial color density.
・耐湿保存性:上記の方法で発色させた試験片を、40
℃、90%R11に調整したタバイ製環境試験器に36
時間放置し、その後の色濃度を上記マクベス濃度計で測
定し、その値の初期発色濃度に対するパーセンテージを
もって感熱記録紙の耐熱保存率(%)を表示した。・Moisture resistance storage property: The test piece colored by the above method was
36°C in a Tabai environmental tester adjusted to 90% R11.
After leaving it for a while, the color density was measured using the Macbeth densitometer mentioned above, and the heat-resistant storage rate (%) of the thermosensitive recording paper was expressed as a percentage of the initial color density.
試験結果を第1表に示す。The test results are shown in Table 1.
実施例2
■ 顔料下塗り紙の調製
焼成りレイ (商品名アンシレックス)85部を、32
0部の水に分散し、得られた分散液にスチレン−ブタジ
ェン共重合エマルジョン(固形分50%)40部、およ
び10%酸化でんぷん水溶液50部を混合した。得られ
た塗液を、坪量48g/m’の原紙の一面上に、乾燥後
の塗布量が7.0g/m’になるよう塗工し乾燥して、
顔料下塗り紙を作成した。Example 2 ■ Preparation of pigmented undercoated paper 85 parts of Baked Ray (trade name: Ansilex) were mixed with 32
The resulting dispersion was mixed with 40 parts of a styrene-butadiene copolymer emulsion (solid content 50%) and 50 parts of a 10% oxidized starch aqueous solution. The obtained coating liquid was applied onto one side of base paper with a basis weight of 48 g/m' so that the coating amount after drying was 7.0 g/m', and dried.
A pigment-primed paper was created.
■ 感熱発色層の形成
A分散液50部、B分散液200部、炭酸カルシウム2
5部、30%パラフィン分散液20部、および10%ポ
リビニルアルコール水溶液180部を混合、攪拌し、塗
布液とした。得られた塗布液を、上記顔料下塗り紙の顔
料塗布面上に、乾燥後の塗布量が5.0g/m’となる
ように塗布し乾燥して、感熱発色層を形成し、感熱記録
紙を得た。この感熱記録紙に、実施例1に記載のテスト
を施した。その結果を第1表に示す。■ Formation of thermosensitive coloring layer 50 parts of dispersion A, 200 parts of dispersion B, 2 parts of calcium carbonate
5 parts of a 30% paraffin dispersion, and 180 parts of a 10% polyvinyl alcohol aqueous solution were mixed and stirred to prepare a coating liquid. The obtained coating liquid is applied onto the pigment-coated surface of the pigment undercoated paper so that the coating amount after drying is 5.0 g/m' and dried to form a heat-sensitive coloring layer, and then the heat-sensitive recording paper is coated with the coating solution. I got it. This thermosensitive recording paper was subjected to the test described in Example 1. The results are shown in Table 1.
実施例3
実施例2と同じ操作を行った。但し、B液の調製におい
て、調製例1の顕色性化合物分子混合物のかわりに、調
製例2の顕色性化合物分子混合物を用いた。テスト結果
を第1表に示す。Example 3 The same operation as in Example 2 was performed. However, in preparing Solution B, the color developer compound molecule mixture of Preparation Example 2 was used instead of the color developer compound molecule mixture of Preparation Example 1. The test results are shown in Table 1.
実施例4
実施例2と同じ操作を行った。但し、B液の調製におい
て、調製例1の分子混合物のかわりに、調製例3の顕色
性化合物分子混合物を用いた。テスト結果を第1表に示
す。Example 4 The same operation as in Example 2 was performed. However, in the preparation of Solution B, the color developer compound molecule mixture of Preparation Example 3 was used instead of the molecule mixture of Preparation Example 1. The test results are shown in Table 1.
実施例5
実施例2と同じ操作を行った。但し、B液の調製におい
て、調製例1の分子混合物のかわりに調製例4の顕色性
化合物分子混合物を用いた。得られた感熱記録紙に、実
施例1に記載のテストの内、発色テストおよび経時変化
テストのみを施した。Example 5 The same operation as in Example 2 was performed. However, in the preparation of Solution B, the color developer compound molecule mixture of Preparation Example 4 was used instead of the molecule mixture of Preparation Example 1. Of the tests described in Example 1, only the color development test and the aging test were performed on the obtained thermosensitive recording paper.
その結果を第1表に示す。The results are shown in Table 1.
実施例6
実施例2と同じ操作を行った。但し、A液の調整におい
て、3−(ジブチルアミン)−6−メチル−7−アニリ
ツフルオランのかわりに、3−(N−イソペンチル−N
−エチルアミノ)−6−メチル−7−アニリツフルオラ
ンを用いた。テスト結果を第1表に示す。Example 6 The same operation as in Example 2 was performed. However, in preparing Solution A, 3-(N-isopentyl-N
-ethylamino)-6-methyl-7-anilite fluoran was used. The test results are shown in Table 1.
比較例1
実施例2と同じ操作を行った。但し、B液の調製におい
て、調製側混合例1の分子混合物11部のかわりに、ビ
スフェノールA10部の分散物を使用した。テスト結果
を第1表に示す。Comparative Example 1 The same operation as in Example 2 was performed. However, in preparing Solution B, a dispersion of 10 parts of bisphenol A was used instead of 11 parts of the molecular mixture in Preparation Mixing Example 1. The test results are shown in Table 1.
比較例2
実施例2と同じ操作を行った。但し、B液の調製におい
て、調製例1の分子混合物11部のかわりに、ビスフェ
ノールA10部を用い、また感熱発色層形成時の塗布液
調製において、別途平均粒径が1m以下に分散した1、
1−ビス(4′−ヒドロキシフェニル)−1−フェニル
−エタン(25重1%分散物)8部をさらに添加した。Comparative Example 2 The same operation as in Example 2 was performed. However, in the preparation of Solution B, 10 parts of bisphenol A was used instead of 11 parts of the molecular mixture in Preparation Example 1, and in the preparation of the coating solution when forming the heat-sensitive coloring layer, 1, which had been separately dispersed with an average particle size of 1 m or less, was used.
A further 8 parts of 1-bis(4'-hydroxyphenyl)-1-phenyl-ethane (25% by weight dispersion) were added.
テスト結果を第1表に示す。The test results are shown in Table 1.
比較例3
比較例1と同じ操作を行った。但し、A液の調製におい
て、3−(ジブチルアミノ)−6−メチル−7−アニリ
ツフルオランのかわりに、3−(N−イソペンチル−N
−エチルアミノ)−6−メチル−7−アニリツフルオラ
ンを用いた。テスト結果を第1表に示す。Comparative Example 3 The same operation as in Comparative Example 1 was performed. However, in the preparation of Solution A, 3-(N-isopentyl-N
-ethylamino)-6-methyl-7-anilite fluoran was used. The test results are shown in Table 1.
第1表から明らかなように、本発明に係る実施例1〜6
の感熱記録紙は、いづれも比較例1〜3の感熱記録紙に
比較して、実用上十分な発色濃度と、よりすぐれた経時
保存率、耐熱保存率および耐顯保存率を示した。As is clear from Table 1, Examples 1 to 6 according to the present invention
All of the thermal recording papers exhibited a practically sufficient color density and better storage rates over time, heat resistance, and stain resistance than the thermal recording papers of Comparative Examples 1 to 3.
本発明の感熱記録紙は、その感熱発色層中に、低融点顕
色性化合物と、高融点顕色性化合物との分子レベルにお
ける混合物からなる顕色剤を含有させることにより、発
色画像の経時、加熱下、および加湿下の保存性を大幅に
向上させることができ、実用上極めて有用なものである
。The heat-sensitive recording paper of the present invention contains a color developer consisting of a mixture at the molecular level of a low-melting point color-developing compound and a high-melting point color-developing compound in the heat-sensitive coloring layer. , storage stability under heating and humidification can be greatly improved, and is extremely useful in practice.
Claims (1)
面に形成され、かつ、無色または淡色の染料前駆体と、
この染料前駆体と加熱下に反応してこれを発色させる顕
色剤とを含む感熱発色層とを有し、 前記顕色剤が、160℃未満の融点を有する少なくとも
1種の顕色性化合物と、160℃以上の融点を有する少
なくとも1種の顕色性化合物との分子レベルにおける混
合物からなることを特徴とする感熱記録体。[Claims] 1. A sheet-like substrate; a colorless or light-colored dye precursor formed on at least one surface of the sheet-like substrate;
a thermosensitive coloring layer comprising this dye precursor and a color developer that reacts with the dye precursor to develop color under heating, the color developer being at least one color developer compound having a melting point of less than 160°C. and at least one color developing compound having a melting point of 160° C. or higher at a molecular level.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1335730A JPH03193490A (en) | 1989-12-25 | 1989-12-25 | Thermal recording material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1335730A JPH03193490A (en) | 1989-12-25 | 1989-12-25 | Thermal recording material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03193490A true JPH03193490A (en) | 1991-08-23 |
Family
ID=18291830
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1335730A Pending JPH03193490A (en) | 1989-12-25 | 1989-12-25 | Thermal recording material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03193490A (en) |
-
1989
- 1989-12-25 JP JP1335730A patent/JPH03193490A/en active Pending
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